An efficient synthesis of polyynyl and polyynediyl complexes of ruthenium(II)

Article abstract of DOI:10.1039/a905174k

The fluoride-induced desilylation of trimethylsilyl-substituted alkynes and polyynes and subsequent reactions with RuCl(PPh₃)₂Cp have been used to synthesize complexes containing unsaturated chains containing up to six carbons. Reactions with Co₂(CO)₈ or tetracyanoethene have been further used to characterise the products. Structural confirmation of RuX(PPh₃)₂Cp [X = C≡CC₆H₄C≡CSiMe₃ 2, C≡CC≡CPh 4, C≡CC₂Ph{Co₂(CO)₆} 8, C≡CC₂H-{Co₂(μ-dppm)(CO)₄} 9, C≡CC{=C(CN)₂}CPh=C(CN)₂ 10 or C≡CC{=C(CN)₂}C{=C(CN)₂}C≡CPh 11] and {Ru(PPh₃)₂Cp}₂(μ-C_n) [n = 4 (6) or 6 (7)] is reported. The Royal Society of Chemistry 1999.

Full text of DOI:10.1039/a905174k

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An efficient synthesis of polyynyl and polyynediyl complexes of
ruthenium(II)†
Michael I. Bruce,a Ben C. Hall,a Brian D. Kelly,a Paul J. Low,a Brian W. Skeltonb and
Allan H. Whiteb
a Department of Chemistry, University of Adelaide, Adelaide, South Australia 5005, Australia.
E-mail: michael.bruce@adelaide.edu.au
b Department of Chemistry, University of Western Australia, Nedlands, Western Australia
6907, Australia
Received 28th June 1999, Accepted 24th August 1999
The fluoride-induced desilylation of trimethylsilyl-substituted alkynes and polyynes and subsequent reactions with
RuCl(PPh3)2Cp have been used to synthesize complexes containing unsaturated chains containing up to six carbons.
Reactions with Co2(CO)8 or tetracyanoethene have been further used to characterise the products. Structural
᎐
᎐
᎐
᎐
᎐
᎐
confirmation of RuX(PPh ) Cp [X = C᎐CC H C᎐CSiMe 2, C᎐CC᎐CPh 4, C᎐CC Ph{Co (CO) } 8, C᎐CC H-
᎐
᎐
᎐
᎐
᎐
᎐
3
᎐
2
6
4
3
2
2
6
2
᎐
᎐
{Co (µ-dppm)(CO) } 9, C᎐CC{᎐C(CN) }CPh᎐C(CN) 10 or C᎐CC{᎐C(CN) }C{᎐C(CN) }C᎐CPh 11] and
᎐
᎐
᎐
᎐
᎐
᎐
᎐
2
4
2
2
2
2
{Ru(PPh3)2Cp}2(µ-Cn) [n = 4 (6) or 6 (7)] is reported.
methanol afforded the alkynyl, diynyl or diynediyl products in
good to excellent yields as yellow or orange microcrystalline
precipitates (Scheme 1). The complexes were readily purified by
chromatography and crystallisation where necessary, and
derivatives could be formed by reaction with Co2(CO)8 or tetra-
cyanoethene (tcne). The new complexes were characterised by
elemental microanalysis and the usual spectroscopic tech-
niques, in addition to single crystal X-ray diffraction studies in
Introduction
Metal complexes containing long unsaturated carbon chains
are currently the subject of intense international interest,
attracting the attention of those concerned with the prepar-
ation of complexes with unusual electronic, magnetic and
optical properties.1 The metal acetylide linkage has proven to be
especially popular in these respects, and consequently the chem-
istry of transition metal alkynyl, diynyl and higher polyynyl
complexes has undergone something of a renaissance, with a
view to the preparation of molecular wires and other nano-
scale devices. Recent developments include the preparation of
an extensive series of complexes which have been shown to have
reasonable non-linear optical properties2 and the synthesis of
interesting luminescent complexes containing metal-capped
carbon chains linked to clusters, such as [Cu3(µ-dppm){µ3-η1-
selected cases (see below).
᎐
In the case of Ru(C᎐CPh)(PPh ) Cp 1, a mixture of RuCl-
᎐
3
2
᎐
(PPh ) Cp, PhC᎐CSiMe and KF was heated in refluxing
᎐
3
2
3
MeOH for a few minutes, when 1 precipitated and could be
isolated by filtration in 84% yield. The product was readily
identified by comparison of its spectral data with those
obtained from an authentic sample.5
᎐
᎐
The related bright yellow Ru(C᎐CC H C᎐CSiMe -4)(PPh ) -
᎐
᎐
6
4
3
3 2
ϩ
3
᎐
᎐
C᎐CC H C᎐C[Re(CO) (bpy)]-4} ] and related complexes.
᎐
᎐
6
4
3
2
᎐
Cp 2 was similarly prepared from 1,4-(Me SiC᎐C) C H ; it
᎐
3
2
6
4
Some of our recent efforts have been directed towards over-
coming the synthetic challenges associated with the preparation
of organometallic compounds in which metal centres are linked
by conjugated bridging ligands of well defined geometry. In
particular, there is a need for synthetic methods which yield
metal acetylide complexes, but do not require the isolation and
manipulation of the parent terminal alkynes. We have recently
described the use of buta-1,3-diyne as a reagent for the prepar-
precipitated from the reaction solution before cleavage of the
᎐
᎐
second ᎐C–SiMe bond could occur. Two ν(C᎐C) bands were
᎐
᎐
3
observed in the IR spectrum at 2155 and 2078 cmϪ1 (Table 1),
the higher energy absorption probably arising from the
1
C᎐CSiMe group. In the H and 13C NMR spectra singlet Cp
᎐
᎐
3
resonances were found at δ 4.30 and 85.21 respectively, while the
retention of an SiMe3 group was evidenced by singlet reson-
ances at δH 0.22 and δC 0.13. The acetylenic carbons were found
at δC 123.46 (Cα, JCP 25 Hz), 116.71, 115.10 and 106.48 while the
ES mass spectrum contained the Mϩ ion at m/z 888.
᎐
᎐
ation of diynyl {ML }C᎐CC᎐CH and both homo and hetero
᎐
᎐
n
᎐
᎐
metallic diynediyl complexes {ML }C᎐CC᎐C{MЈLЈ } using a
᎐
᎐
m
n
copper() catalyst.4 While this has proven to be a versatile
method for the preparation of M(CO)nCp derivatives, the reac-
tion sequence failed when applied to more electron-rich metal
centres such as RuCl(PPh3)2Cp and RuCl2(dppm)2. This limit-
ation, coupled with the obvious need for extreme caution when
The remaining acetylenic SiMe3 group in complex 2 was also
amenable to metallation. Thus, subsequent treatment of 2 with
RuCl(PPh3)2Cp also in the presence of KF, carried out in a
solvent mixture of thf–MeOH in which the solubility of 2
was improved, afforded the orange binuclear complex 1,4-
manipulating buta-1,3-diyne, prompted us to examine the use
of acetylenic synthons bearing masked C᎐CH functionalities.
᎐
᎐
{Cp(PPh ) Ru(C᎐C)} C H 3 in 43% yield. A single ν(C᎐C)
᎐
᎐
3
2
2
6
4
᎐
band was found in the IR spectrum at 2089 cmϪ1, while the
chemically equivalent Cp ligands gave rise to only one singlet
resonance in each of the 1H (δH 4.34) and 13C (δC 85.15) NMR
spectra. The acetylenic carbons were found at δC 115.10 and
106.40. Owing to the relatively poor solubility of 3 in common
solvents, the signal-to-noise ratio in the 13C spectrum was
low, and the expected coupling to phosphorus could not be
resolved. The ES mass spectrum contained Mϩ at m/z 1506, and
a fragment ion at m/z 720 representing the loss of three PPh3
ligands was also present.
᎐
Results
The reactions of RuCl(PPh3)2Cp with the trimethylsilyl-
᎐
᎐
protected alkynes Me SiC᎐CR (R = Ph, C H C᎐CSiMe -4,
᎐
᎐
3
6
4
3
᎐
᎐
᎐
᎐
᎐
᎐
C᎐CPh, C᎐CSiMe , C᎐CC᎐CPh or C᎐CC᎐CSiMe ) and KF in
᎐
᎐
᎐
᎐
᎐
᎐
3
3
† Supplementary data available: rotatable 3-D crystal structure diagram
in CHIME format. See http//www.rsc.org/suppdata/dt/1999/3719/
J. Chem. Soc., Dalton Trans., 1999, 3719–3728
This journal is © The Royal Society of Chemistry 1999
3719

View Article Online
Table 1 Analytical and spectroscopic data
Complex/analysis
IR/cmϪ1
NMR
ES MS m/z
(MeOH): 888, Mϩ
2 Ru(C᎐CC6H4C᎐CSiMe3)(PPh3)2Cp
(Nujol): ν(CC)
2155s, 2078s
1H NMR (CDCl3): δ 0.22 (SiMe3, s, 9
H), 4.30 (Cp, s, 5 H), 7.0–7.50 (aryl H,
m, 30 H)
᎐
᎐
᎐
᎐
Found: C, 72.43; H, 5.39. Calc. for
C54H48P2RuSi: C, 72.20; H, 5.59%
M 888
13C NMR (CDCl3): δ 0.13 (s, SiMe3),
85.21 (s, Cp), 106.48, 115.10, 116.71
᎐
(3 × s, C᎐C), 123.46 (t, JCP 25 Hz,
᎐
Ru–C), 127.54–138.96 (m, Ph)
᎐
3 1,4-{Cp(PPh3)2Ru(C᎐C)}2C6H4
(Nujol): ν(CC) 2089s
1H NMR (CDCl3): δ 4.34 (Cp, s, 10 H), (MeOH): 1506, Mϩ; 720,
᎐
Found: C, 72.56; H, 5.49. Calc. for
C92H74P4Ru2ؒMeOH: C, 72.64; H, 5.11%
M 1506
6.97–7.50 (Ph, m, 64 H)
[M Ϫ 3PPh3]ϩ; 690,
[Ru(PPh3)2Cp]ϩ
13C NMR (CDCl3): δ 85.15 (s, Cp),
106.40 (s, C), 115.10 (s, C), 127.15–
138.98 (m, Ph)
1H NMR (CDCl3): δ 4.35 (s, 5 H, Cp),
7.11–7.46 (m, 35 H, Ph)
(MeOH ϩ NaOMe): 839,
[M ϩ Na]ϩ
᎐
᎐
᎐
(CH2Cl2): ν(C᎐C)
᎐
2162s, 2025s
4 Ru(C᎐CC᎐CPh)(PPh3)2Cp
᎐
᎐
Found: C, 74.59; H, 4.87. Calc. for
C51H40P2Ru: C, 75.07; H, 4.94%
M 816
13C NMR (CDCl3): δ 62.87 (Cγ, Cδ),
80.47 (t, JCP 11.0, Cα), 85.71 (t, JCP 8.4
Hz, Cp), 95.64, 102.40 (Cβ, Cγ or Cδ),
126.00–138.78 (m, Ph)
1H NMR (CDCl3): δ 4.36 (s, 5 H, Cp),
7.10–7.43 (m, 35 H, Ph)
᎐
᎐
᎐
᎐
(CH2Cl2): ν(C᎐C)
᎐
1996s, 2108s, 2151m
᎐
(CHCl3): ν(C᎐C)
᎐
5 Ru(C᎐CC᎐CC᎐CPh)(PPh3)2Cp
᎐
᎐
᎐
1H NMR (CDCl3): δ 4.29 (s, 10 H, Cp), (MeOH): 1454, [M]ϩ; 1192,
᎐
᎐
᎐
7 {Ru(PPh3)2Cp}2(µ-C᎐CC᎐CC᎐C)
᎐
᎐
᎐
Found: C, 69.63; H, 4.78. Calc. for
C88H70P4Ru2ؒCH2Cl2: C, 69.47; H, 4.72%
M 1454
2135w, 2066s, 1965w
7.07–7.46 (m, 60 H, Ph)
[M Ϫ PPh3]ϩ; 930,
[M Ϫ 2PPh3]ϩ
1H NMR (CDCl3): δ 4.34 (s, 5 H, Cp),
7.04–7.65 (m, 35 H, Ph)
(MeOH ϩ NaOMe): 1133,
[M ϩ OMe]Ϫ
᎐
᎐
8 Ru{C᎐CC2Ph[Co2(CO)6]}(PPh3)2Cp
(cyclohexane): ν(C᎐C)
᎐
᎐
Found: C, 58.07; H, 3.63. Calc. for C57H40-
Co2O6P2RuؒCH2Cl2: C, 58.70; H, 3.57%
M 1102
2079w, ν(CO) 2040s,
2012 (br) s, 1996w
1H NMR (CDCl3): δ 4.62 (s, 5 H, Cp),
7.09–7.37 (m, 35 H, Ph)
(MeOH): 945, [M ϩ H]ϩ
᎐
10 Ru{C᎐CC[᎐C(CN)2]CPh᎐C(CN)2}(PPh3)2Cp
Found: C, 68.08; H, 4.64; N, 5.20. Calc. for
C57H40N4P2RuؒCH2Cl2: C, 67.70; H, 4.11;
(CH2Cl2): ν(CN) 2214m,
᎐
᎐
᎐
᎐
ν(C᎐C) 1980s (br)
᎐
13C NMR (CDCl3): δ 80.47 [t, J(CP)
11.0 Hz, Cα], 83.48, 88.94 (2 × Cp),
112.21, 112.88, 114.84, 116.16
(4 × CN), 127.79–146.45 (m, Ph)
1H NMR (CDCl3): δ 4.61 (s, 5 H, Cp),
7.14–7.32 (m, 35 H, Ph)
N, 5.44%
M 944
᎐
᎐
11 Ru{C᎐CC[᎐C(CN)2]C[᎐C(CN)2]C᎐CPh}-
(CH2Cl2): ν(CN)
2214w, 2183m; ν(C᎐C)
(MeOH ϩ NaOMe): 991,
[M ϩ Na]ϩ
᎐
᎐
᎐
᎐
᎐
(PPh3)2Cp
᎐
Found: C, 72.92; H, 4.78; N, 5.29. Calc. for
C59H40N4P2Ru: C, 73.20; H, 4.16; N, 5.79%
M 968
1984s (br)
1H NMR (CDCl3): δ 4.35 (s, 10 H, Cp), (CH2Cl2–MeOH): 1583
5.32 (s, 2 H, CH2Cl2), 7.12–7.35 (m, 60
᎐
12 {Ru(PPh3)2Cp}2{µ-C᎐CC[᎐C(CN)2]2}
(Nujol): ν(CN) 2213m,
᎐
᎐
Found: C, 68.58; H, 4.42; N, 3.40. Calc. for
ν(C᎐C) 1987s, 1967s,
[M]ϩ
᎐
᎐
C94H70N4P4Ru2ؒCH2Cl2: C, 68.45; H, 4.35;
1714m
H, Ph)
N, 3.36%
M 1582
Scheme 1 [Ru] = Ru(PPh3)2Cp.
᎐
᎐
᎐
The reaction of Me SiC᎐CC᎐CPh with RuCl(PPh ) Cp and
contained the expected resonances, with the diynyl carbons
giving rise to resonances at δC 80.47 (Cα, JCP 11 Hz), 81.42 (Cβ),
95.64 and 102.40 (Cγ and Cδ). The IR spectrum contained two
᎐
3
3 2
KF in methanol yielded a pale green-yellow precipitate from
᎐
᎐
which the yellow diynyl complex Ru(C᎐CC᎐CPh)(PPh ) Cp 4
᎐
᎐
3
2
was isolated in good yield (75%). The 1H and 13C NMR spectra
discrete ν(C᎐C) absorptions at 2025 and 2162 cm . The elec-
Ϫ1
᎐
᎐
3720 J. Chem. Soc., Dalton Trans., 1999, 3719–3728

View Article Online
trospray (ES) mass spectrum collected from solutions contain-
ing NaOMe, or KF, showed formation of aggregates with the
alkali metal cations, the ions [M ϩ Na]ϩ and [M ϩ K]ϩ, respec-
tively, being observed.6
between 1965 and 2135 cmϪ1, a sharp δH resonance at 4.29,
and the observation of the molecular ion at m/z 1454 in the ES
mass spectrum. Fragment ions consistent with the sequential
loss of two PPh3 ligands were also present at m/z 1192 and 930.
᎐
᎐
᎐
The triyne Me SiC᎐CC᎐CC᎐CPh was prepared by Sono-
We have shown previously that complexation of one or more
᎐
᎐
᎐
3
7
᎐
᎐
᎐
᎐
gashira coupling of Me SiC᎐CC᎐CH with IC᎐CPh in moder-
C᎐C triple bonds in polyynylmetal complexes with Co (CO) or
᎐
᎐
᎐
᎐
3
2
6
ate (29%) yield. The SiMe3 protecting group gave rise to a high
field singlet at δ 0.22 in the H NMR spectrum, while the IR
Co2(µ-dppm)(CO)4 fragments affords derivatives which often
crystallise more readily than the parent compounds and enable
structural confirmation of the presence of the Cn chain to be
1
᎐
spectrum contained three ν(C᎐C) bands at 2075, 2174 and 2195
᎐
Ϫ1
cm . The reaction between RuCl(PPh ) Cp and Me SiC᎐
CC᎐CC᎐CPh with KF in methanol afforded a dark coloured
obtained.9 Treatment of complex 4 with Co2(CO)8 afforded
᎐
᎐
3
2
3
᎐
᎐
᎐
black crystals of Ru{C᎐CC Ph[Co (CO) ]}(PPh ) Cp 8, in
᎐
᎐
᎐
2
2
6
3 2
solution, which was shown to contain the triynyl complex
which the dicobalt fragment was shown to be attached to the
C2 fragment adjacent to the Ph group by a single-crystal
1
᎐
᎐
᎐
Ru(C᎐CC᎐CC᎐CPh)(PPh ) Cp 5 by H NMR and IR spec-
᎐
᎐
᎐
3
2
troscopy. The presence of ca. 10% unchanged RuCl(PPh3)2Cp
was established by the presence of the characteristic Cp reson-
ance at δH 4.10 in the NMR spectrum. Purification of the com-
plex was complicated by its ready decomposition on both Al2O3
and silica gel; mass spectroscopic characterisation could not be
X-ray determination (see below). A similar complex had been
᎐
obtained previously from the reaction of HC᎐CC H[Co -
᎐
2
2
(µ-dppm)(CO)4] with RuCl(PPh3)2Cp in the presence of 1,8-
diazabicyclo[5,4,0]undec-7-ene(dbu),10 but until the recent
acqusition of a CCD area detector facility the product had
achieved, despite the use of various chemical ionisation aids.
defied structural characterisation. This complex has now been
᎐
᎐
The reaction between the bis(trimethylsilyl)diyne Me SiC᎐
identified as Ru{C᎐CC H[Co (µ-dppm)(CO) ]}(PPh ) Cp 9.
᎐
᎐
3
2
2
4
3 2
᎐
CC᎐CSiMe , two equivalents of RuCl(PPh ) Cp and KF in
Since 9 exhibits structural elements similar to the other com-
pounds described herein its structure is described below for
comparative purposes.
᎐
3
3 2
methanolgavethebis(ruthenium)diynediylcomplex{Ru(PPh3)2-
᎐
᎐
Cp} (µ-C᎐CC᎐C) 6 as a microcrystalline orange material in
᎐
᎐
2
good overall yield (ca. 70%). We noted an increased yield of 6
when the reaction mixture contained an additional amount of a
base, such as NEtCy2. The complex was characterised by com-
parison of the spectral data with those previously reported,8
Tetracyanoethene (tcne) is known to undergo rapid reactions
with many acetylide complexes of transition metals, to give
stable crystalline derivatives.11 These derivatives are occasion-
ally more suitable for structural analysis than the parent com-
plex. The reaction of 4 with tcne afforded deep red crystals of
Ϫ1
᎐
including the ν(C᎐C) band at 1970 cm , a single Cp resonance
᎐
at δH 4.17 and the observation of both Mϩ (m/z 1430) and M2ϩ
(m/z 715) ions in the ES mass spectrum. Adjusting the stoichio-
metry of the reaction had no effect on the nature of the product
Ru{C᎐CC[᎐C(CN) ]CPh᎐C(CN) }(PPh ) Cp 10, which was
᎐
᎐
᎐
᎐
2
2
3 2
characterised as the mono adduct by elemental analyses and
the electrospray (ES) mass spectrum, which gave [M ϩ H]ϩ at
᎐
᎐
and attempts to prepare the diynyl complexes Ru(C᎐CC᎐CR)-
m/z 945, while the site of addition was confirmed as the
᎐
᎐
᎐
(PPh3)2Cp (R = H or SiMe3) from reactions of RuCl(PPh3)2Cp
C᎐C triple bond adjacent to the Ph group by an X-ray
᎐
᎐
᎐
with an excess of Me SiC᎐CC᎐CSiMe resulted only in the
determination.
᎐
᎐
3
3
isolation of 6.
Similar reactions of complexes 5 and 7 with an excess of tcne
᎐
᎐
Our previous study described the synthesis of complex 6
from the reaction of Ru(thf)(PPh3)2Cp with one half equivalent
of the dilithiodiacetylide LiC᎐CC᎐CLi. At that time, we iden-
afforded Ru{C᎐CC[᎐C(CN) ]C[᎐C(CN) ]C᎐CPh}(PPh ) Cp 11
᎐
᎐
᎐
᎐
᎐
᎐
2
2
3
2
᎐
᎐
and {Ru(PPh ) Cp} {µ-C᎐CC[᎐C(CN) ]C[᎐C(CN) ]C᎐C} 12,
᎐
᎐
3
2
2
2
2
8
᎐
᎐
respectively, the structure of the former being unequivocally
characterised by an X-ray determination. In the case of the
reaction with 7 the initial orange solution deepened to dark red
over 30 min. Purification of the reaction mixtures by prepar-
ative TLC afforded green-black and dark red bands which
yielded 11 and 12, respectively, following crystallisation from
dichloromethane–methanol mixtures.
᎐
᎐
tified two rotamers of this complex in which the Cp rings were
disposed in either cis (6-cis) or trans (6-trans) fashion about
᎐
᎐
the C᎐CC᎐C ligand, although we were then unable to establish
᎐
᎐
selective preparations of these structural isomers, the details of
their interconversion, or any distinguishing spectral properties.
Crystallisation of complex 6 by either slow evaporation of a
concentrated CH2Cl2 solution or by vapour diffusion of diethyl
ether into a thf solution afforded orange crystals of the cis
The IR spectrum of complex 11 contained two ν(CN) bands
Ϫ1
᎐
at 2214 and 2183 cm , as well as a strong ν(C᎐C) or ν(C᎐C᎐C)
᎐
᎐ ᎐
band at 1984 cmϪ1. The Cp ligand gave rise to a sharp singlet at
᎐
isomer 6-cis which is characterised by a single ν(C᎐C) band in
᎐
the IR spectrum (Nujol) at 1970 cmϪ1. A single crystal structure
determination using crystals obtained from dichloromethane
was of the cis form;8 that study is augmented by the two further
studies recorded herein (see below).
δH 4.61. The addition reaction was shown to have occurred at
᎐
the central C᎐C moiety by a single crystal X-ray diffraction
᎐
study (see below). A degree of symmetry in complex 12 was
1
evidenced by the presence of a singlet Cp resonance in the H
When a thf solution of complex 6-cis prepared as above was
NMR spectrum (δH 4.35) and only a single ν(CN) band in the
IR spectrum. The ES mass spectrum contained the [M]ϩ ion
m/z 1583, and the [M Ϫ PPh3]ϩ fragment ion at m/z 1321.
allowed to stand undisturbed large crystals of the second iso-
mer, shown previously to be 6-trans,8 were deposited from solu-
᎐
tion. This isomer is characterised by the presence of two ν(C᎐C)
᎐
bands in the IR spectrum (Nujol) at 1990w and 1976m cmϪ1. As
might be expected, the structural isomers readily and repro-
ducibly interconvert with no loss of material. Thus, a sample of
6-cis could be taken up in hot thf and allowed to crystallise
thereby yielding 6-trans. Conversely, recrystallisation of 6-trans
Molecular structures
The molecular structures of several of the complexes described
above have been determined by single crystal X-ray studies
and are best described by comparison of the main structural
features present in each molecule with those of related alkynyl
and diynyl compounds and derivatives. In all cases the geom-
etries of the Ru(PPh3)2Cp fragments are closely similar to
those of the many other examples in the literature,12 the struc-
tural parameters (Table 2) being within the ranges: Ru–P
2.283(3)–2.333(1); Ru–C(cp) 2.202(6)–2.273(4) (av. 2.22–
2.25) Å; P–Ru–P 99.02(5)–102.94(4), P–Ru–C 85.8(4)–95.1(2)Њ,
consistent with a slightly distorted octahedral geometry about
ruthenium, considering the Cp ligand to be occupying three co-
ordination sites. One molecule comprises the asymmetric unit
from CH2Cl2 afforded 6-cis. The solution IR spectra of both
᎐
isomers in CH Cl were identical, with a single ν(C᎐C) band
᎐
2
2
at 1969 cmϪ1. Likewise, NMR spectra in CDCl3 were indis-
tinguishable and only one Cp environment was detected at
room temperature.
᎐
᎐
The analogous triynediyl complex {Ru(PPh ) Cp} (µ-C᎐CC᎐
CC᎐C) 7 was prepared in a similar fashion to 6 from RuCl-
(PPh ) Cp and Me SiC᎐CC᎐CC᎐CSiMe . The structural deter-
᎐
᎐
3
2
2
᎐
᎐
᎐
᎐
᎐
᎐
᎐
᎐
3
2
3
3
mination described below showed it to have the trans con-
᎐
formation. Complex 7 was characterised by ν(C᎐C) bands
᎐
J. Chem. Soc., Dalton Trans., 1999, 3719–3728
3721

View Article Online
Fig. 1 Projections of single molecules of complexes (a) 2, (b) 4, (c) 6-cis [(i) thf and (ii) MeOH solvates], (d)–(h) 7–11 respectively. Ellipsoids are
shown at the 20 (room temperature) and 50% (low temperature) levels, as appropriate. For 11, only molecule 1 is depicted.
in all cases, except 6ؒMeOH and 7 (where a half molecule,
disposed about a crystallographic 2 axis or inversion centre,
respectively) and 11 (two molecules).
furthest from the ruthenium, perhaps as a result of steric con-
straints imposed by the two PPh3 ligands. The Ru–C(1) separ-
ations are 1.985(4) (8) and 2.01(2) Å (9), the former perhaps
being slightly shorter than that found in precursor 4. The
᎐
᎐
᎐
(a) Ru(C᎐CC H C᎐CSiMe -4)(PPh ) Cp 2. A molecule of
uncomplexed C᎐C triple bond in 8 [1.227(5) Å] is slightly longer
᎐
᎐
᎐
6
4
3
3 2
complex 2 is shown in Fig. 1(a). It is appropriate to compare the
than in 4, but that in 9 [1.19(3) Å] appears normal. Angles at
C(1) and C(2) are 171.3(2) and 176.7(2)Њ in 8, 168(2) and 177(2)Њ
5
᎐
structure with that of Ru(C᎐CPh)(PPh ) Cp 1, from which
᎐
3
2
there is little significant difference. Thus the Ru–C(1) and C(1)–
C(2) distances are respectively 2.021(6), 1.173(9), and 2.017(5),
in 9, the former values showing two of the largest distortions
᎐
observed in a σ-bonded C᎐C unit. The usual lengthening of the
᎐
1.214(7) Å for the two complexes, with angles at C(1) and C(2)
complexed C(3)–C(4) moiety [to 1.354(5) in 8, 1.32(3) Å in 9]
results from the back bonding from the Co2 fragment; associ-
ated bend-back angles at C(3) and C(4) are 140.0(3) and
135.1(3)Њ (8) and 145(2)Њ [at C(3) in 9].
᎐
of 177.5(7), 171.8(8) and 177.4(4), 170.6(5)Њ. In the C᎐CSiMe
᎐
3
᎐
fragment of 2 the C᎐C and Si–C bond lengths are 1.21(1) and
᎐
1.817(8) Å, with angles at C(2041) and C(2042) of 177(1) and
174.2(9)Њ, respectively. These parameters are within previously
measured ranges, the most notable difference being the barely
significant shortening of the C(1)–C(2) bond compared with
that in the phenylethynyl complex.
᎐
᎐
᎐
(c) {Ru(PPh ) Cp} (ꢀ-C᎐CC᎐C)
6
and {Ru(PPh3)2Cp}2-
᎐
3
2
2
᎐
᎐
᎐
(ꢀ-C᎐CC᎐CC᎐C) 7. Comparison of the cis forms of complex 6,
᎐
᎐
᎐
here and as described earlier, shows that the lengths of compar-
able bonds are experimentally identical, with the possible excep-
tion of C(2)–C(2Ј), which is 1.39(1) in the present MeOH sol-
vate, 1.370(6) Å in the trans isomer. There are small differences
in angles at the ruthenium atom in the two isomers, with the C4
chain being somewhat more linear in the trans isomer.
In complex 7, containing the longer carbon chain, steric
interference between PPh3 ligands on the two metal centres is
further diminished and the molecule adopts a trans conform-
᎐
᎐
᎐
᎐
(b) Ru(C᎐CC᎐CPh)(PPh ) Cp 4, Ru{C᎐CC Ph[Co (CO) ]}-
᎐
᎐
3
2
2
2
6
᎐
(PPh ) Cp 8 and Ru{C᎐CC H[Co (ꢀ-dppm)(CO) ]}(PPh ) Cp 9.
᎐
3
2
2
2
4
3 2
Figs. 1(b), 1(e) and 1(f) contain plots of molecules of 4, 8 and 9,
respectively. In 4 atom separations along the RuC4 chain are
᎐
1.994(4), 1.206(5), 1.389(6) and 1.200(6) Å, the two C᎐C bonds
᎐
being essentially identical. Angles at carbons C(1), C(2), C(3)
and C(4) are 178.3(3), 169.5(4), 175.9(4) and 176.9(4)Њ, so that
the chain shows marked non-linearity. In the cobalt derivatives
ation. Structural parameters are similar to those of 6, the cen-
᎐
᎐
8 and 9 the dicobalt fragment is attached to the C᎐C triple bond
tral C᎐C triple bond being identical with the two outer ones.
᎐
᎐
3722
J. Chem. Soc., Dalton Trans., 1999, 3719–3728

View Article Online
Table 2 Selected structural data
(a) The ruthenium environments
Distance/Å
Angles (subtending atoms)/Њ
C(0) ؒ ؒ ؒ P(1) C(0) ؒ ؒ ؒ P(2) C(0) ؒ ؒ ؒ C C ؒ ؒ ؒ P(1) C ؒ ؒ ؒ P(2) P ؒ ؒ ؒ P
Compound
(molecule)
Ru–C(0)
Ru–C(1)
Ru–P(1)
Ru–P(2)
2
1.880
1.896
1.89
1.87
2.021(6)
1.994(4)
2.00(1)
2.01(1)
2.00(1)
2.001(6)
1.985(4)
2.01(2)
1.947(8)
1.935(5)
1.927(5)
2.299(2)
2.296(1)
2.304(3)
2.289(4)
2.283(3)
2.297(2)
2.2947(7)
2.292(6)
2.305(2)
2.308(1)
2.315(1)
2.287(2)
2.333(1)
2.276(5)
2.284(4)
2.296(4)
2.301(1)
2.2873(8)
2.289(5)
2.299(2)
2.306(1)
2.310(1)
122.6
121.2
123.7
120.6
121.7
123.0
124.0
122.0
121.5
123.0
123.4
123.8
121.2
121.8
124.4
123.7
122.7
122.2
123.7
124.0
120.6
123.6
122.6
127.0
124.6
123.3
123.2
121.1
121.0
119.5
122.4
123.2
121.0
89.4(2)
87.3(1)
86.7(1)
90.8(3)
90.0(3)
87.8(2)
90.63(8)
88.6(5)
91.8(2)
88.7(1)
89.7(1)
87.0(2)
88.7(1)
89.0(5)
85.8(4)
86.5(3)
95.1(2)
89.42(9)
92.3(5)
87.8(2)
90.4(1)
90.3(1)
101.77(8)
102.94(4)
101.7(1)
102.7(1)
102.4(1)
99.02(5)
100.82(2)
102.3(2)
100.86(8)
102.67(4)
99.76(5)
4
6/thf(1)
(2)
/MeOH(1) 1.88
7
8
9
1.883
1.89
1.88
1.901
1.902
1.904
10
11(1)
(2)
(b) The alkynyl string; carbon atoms are denoted by number only
1–2
2–3(X)
3–4
4–5/X
1
2
3
4
2
1.173(9)
1.206(5)
1.20(2)
(1.463(9))
1.389(6)
1.38(2)
177.5(7)
178.3(3)
177(1)
171.8(8)
169.5(4)
178(2)
4
1.200(6)
1.25(2)
1.416(6)
175.9(4)
175(1)
176.9(4)
170(1)
6/thf
/MeOH
1.22(1)
1.39(1)
175(1)
177(1)
7
8
1.210(8)
1.227(5)
1.19(3)
1.21(1)
1.237(6)
1.227(7)
1.382(8)
1.394(5)
1.43(3)
1.40(1)
1.372(6)
1.377(7)
1.212(8)
1.354(5)
1.32(3)
1.51(1)
1.384(6)
1.378(7)
172.2(4)
171.3(2)
168(2)
169.4(7)
173.1(4)
170.5(4)
178.8(6)
176.7(2)
177(2)
170.5(9)
170.5(5)
168.6(4)
177.3(6)
140.0(3)
145(2)
116.9(6)
123.7(4)
124.0(4)
1.460(3)
1.35(1)
135.1(3)
118.4(7)
9
10
11(1)
(2)
Also: 2, C(2041)–C(204,2042) 1.44(1), 1.21(1); Si–C(2042), 1.817(8) Å; angles at C(2041,2042): 177(1), 174.2(9)Њ; 8, C(3)–Co(2,3) 2.001(4), 1.993(4);
C(4)–Co(2,3) 1.942(3), 1.956(3); Co(2)–Co(3) 2.4758(7) Å; Co(2)–C(3,4)–Co(3) 76.6(1), 78.85(9); C(3)–Co(2,3)–C(4) 40.1(1), 40.1(1); C(3)–Co(2,3)–
Co(3,2) 51.6(1), 51.8(1); C(4)–Co(2,3)–Co(3,2) 50.83(9), 50.33(9)Њ; 9, C(3)–Co(2,3) 1.96(2), 2.00(2); C(4)–Co(2,3) 1.93(2), 1.98(2); Co(2)–Co(3)
2.451(5) Å; Co(2)–C(3,4)–Co(3) 76.4(8), 77.7(8); C(3)–Co(2,3)–C(4) 39.6(9), 39(1); C(3)–Co(2,3)–Co(3,2) 52.6(9), 51.0(5); C(4)–Co(2,3)–Co(3,2)
51.9(7), 50.4(6)Њ; Co(2)–P(3) 2.213(7); Co(3)–P(4) 2.212(8) Å; P(3)–C(0)–P(4) 110(1); C(0)–P(3)–Co(2) 109.4(6); C(0)–P(4)–Co(3) 110.1(8); P(3)–
Co(2)–C(3,4), Co(3) 132.8(7), 93.5(7), 99.5(2); P(4)–Co(3)–C(3,4), Co(2) 134.2(7), 97.7(7), 94.0(2)Њ; 10, C(4)–C(411) 1.46(1); C(5)–C(51,52) 1.45(1),
᎐
1.45(1); C(3)–C(6) 1.386(9); C(6)–C(61,62) 1.41(1) (×2); C᎐N(51,52,61,62) 1.15(1), 1.12(1), 1.15(1), 1.11(1) Å; angles at C(51,52,61,62) 176.6(9),
᎐
178(1), 179(1), 177(1), C(411)–C(4)–C(3,5) 116.4(7), 125.0(8); C(4)–C(5)–C(51,52) 122.1(8), 123.0(8); C(3)–C(6)–C(61,62) 118.0(7), 123.3(8); C(6)–
C(3)–C(2,4) 123.8(8), 119.2(7)Њ; 11, molecules 1(2), C(4)–C(41,42) 1.423(7), 1.418(6) (1.438(6), 1.432(7)); C(3)–C(5) 1.521(7) (1.511(6)); C(5)–C(6,7)
1.332(6), 1.430(6) (1.369(7), 1.409(6)); C(6)–C(61,62) 1.427(7), 1.455(8), (1.426(6), 1.444(7)); C(7)–C(8) 1.170(7) (1.177(6)); C(8)–C(81) 1.452(7)
᎐
(1.462(9)); C᎐N(41,42,61,62) 1.150(7), 1.152(6), 1.152(7), 1.136(8), (1.136(6), 1.141(7), 1.142(6), 1.139(7)) Å; angles at C(41,42,61,62) 176.3(5),
᎐
176.8(5), 177.3(6), 178.9(6) (178.0(6), 178.4(5), 179.3(6), 179.2(6)); at C(7,8) 176.2(5), 173.8(5) (173.7(5), 172.2(6)); C(3)–C(4)–C(41,42) 119.3(4),
121.4(4) (119.6(4), 123.6(4)); C(41)–C(4)–C(42) 119.3(4) (116.7(4)); C(6)–C(5)–C(7) 121.0(5) (122.4(4)); C(3)–C(5)–C(6,7) 122.1(4), 116.9(4)
(120.3(4), 116.9(4)); C(5)–C(6)–C(61,62) 123.6(5), 119.9(5) (122.0(4), 121.4(4)); C(61)–C(6)–C(62) 116.5(4) (116.6(4))Њ.
There is a more pronounced bending of the C6 chain at C(1)
[172.2(4)Њ] and, somewhat surprisingly, one of the P–Ru–C
angles has opened to 95.1(2)Њ, with a concomitant but lesser
contraction of the P–Ru–P angle to 99.02(5)Њ. These minor
changes (compared with 6) probably result from intermolecular
interactions. Whereas 7, disposed about a crystallographic
inversion centre, is obligate trans, 6 is found in two distinct
phases, as different solvates, both cis; in the more precisely
determined structure the molecule is disposed about a crystal-
lographic 2 axis. These complement the previous study8 which
presented 6 in both cis and trans forms, the present MeOH
solvate being an improved definition of the cis phase.
respectively], while the C(1)–C(2) bonds are either similar
or longer [1.21(1) Å in 10, 1.237(6), 1.227 Å in 11]. In 11, C(7)–
᎐
C(8) are 1.170(7), 1.177(6) Å, at the short end of the C᎐C triple
᎐
bond length range. Angles at C(1) and C(2) are between 169.4
and 173.1(4) (molecule 1), 173.7(5), 172.2(6)Њ (molecule 2),
because of the steric interactions between the PPh3 ligands
and the cyanocarbon substituents whereas at C(7) and C(8)
values of 176.2, 173.7 and 173.8(5)Њ, 172.2, respectively, are
found. Overall, angles within the dicyanomethylene groups are
less than 120Њ as a result of some delocalisation of electron
density within these groups, while angles at C(3) involving
other carbon chain atoms are between 115.4(4) and 120.5(4)Њ.
In 10 the dihedral angle between the planes defined by
C(2,3,4)CN(61,62) and C(3,4,411,5)CN(51,52) is 66.4(2)Њ, the
associated phenyl C6 dihedral to the latter being 39.7(3)Њ; in
11 the dihedral angle between the planes defined by C(3,5–7)-
CN(61,62) and C(2–5)CN(41,42) is 63.2(1) (molecule 1),
75.0(1)Њ (molecule 2).
᎐
(d) Ru{C᎐CC[᎐C(CN) ]CPh᎐C(CN) }(PPh ) Cp 10 and Ru-
᎐
᎐
᎐
᎐
2
2
3 2
᎐
{C᎐CC[᎐C(CN) ]C[᎐C(CN) ]C᎐CPh(PPh ) Cp 11. Figs. 1(g)
᎐
᎐
᎐
᎐
2
2
3 2
and 1(h) contain plots of molecules of complexes 10 and 11.
These complexes are formed by cycloaddition of the electron-
᎐
deficient olefin to the second C᎐C triple bond out from the
᎐
ruthenium, followed by ring opening of the cyclobutene to
give the trans-buta-1,3-dienyl derivatives described here. The
latter group has been described on several previous occasions,
Discussion
the closest analogue being Ru{C[᎐C(CN) ]CPh᎐C(CN) }-
Many metal acetylide complexes may be prepared by deproton-
ation of the corresponding mono-substituted vinylidene com-
plexes [{ML }᎐C᎐CHR]ϩ. In turn, the vinylidene complexes are
᎐
᎐
2
2
(dppe)Cp.11 Comparable structural parameters in the latter are
᎐
similar to those found in 10 and 11. Within the RuC᎐C moieties
᎐
᎐ ᎐
n
the Ru–C bonds are significantly shorter than those found in
the other complexes above [1.947(8), 1.935(5) and 1.927(5) Å,
conveniently obtained from the reactions of terminal alkynes
with metal complexes containing a labile ligand via a 1,2-H
J. Chem. Soc., Dalton Trans., 1999, 3719–3728
3723

View Article Online
Scheme 2
shift.13 However, attempts to prepare polyynyl complexes
The Lapinte group has proposed the mechanism shown in
Scheme 2 to explain the formation of their complexes.25 Initial
desilylation of the trimethylsilyl-substituted acetylene by fluor-
ide ion generates the terminal acetylene in situ, together with an
equivalent amount of the strong base KOMe. The KPF6 salt
acts as a halide abstractor and helps promote co-ordination of
the terminal alkyne to the metal centre leading to the formation
of an intermediate vinylidene complex. Finally, the vinylidene
cation is deprotonated by KOMe yielding the acetylide complex
as the final product.
᎐
{ML }(C᎐C) R via similar reactions are hampered by the
᎐
n
n
formation of highly reactive complexes containing cumulated
ligands from reactions between various metal species and
terminal polyynes H(C᎐C) R,14 and consequently this approach
᎐
᎐
n
has met with only limited success.14b,15
Alkynyl and dialkynyl carbanions are sufficiently nucleo-
philic to displace labile ligands, such as a halide, from a variety
of transition metal complexes to give metal acetylide or
diacetylide complexes.16 The reactions of 1-alkynes with an
appropriate metal substrate in the presence of a copper()
catalyst is widely recognised as a useful procedure for the
formation of metal acetylide complexes,17 and these conditions
have been applied with some success to the preparation of
higher polyynyl complexes and polyynediyl polymers.18
Several successful synthetic schemes incorporating the use of
trialkylstannyl-protected diyne reagents have been described,
A similar mechanism may be invoked to explain the form-
᎐
᎐
ation of Ru(C᎐CPh)(PPh ) Cp from Me SiC᎐CPh and
᎐
᎐
3
2
᎐
3
᎐
᎐
᎐
᎐
4
{Ru(PPh ) Cp} (µ-C᎐CC H C᎐C-4) from Ru(C᎐CC H C᎐
᎐
᎐
᎐
3
2
2
6
4
6
CSiMe3-4)(PPh3)2Cp, as described above. However, the form-
᎐
ation of the complexes Ru{(C᎐C) Ph}(PPh ) Cp from Me -
᎐
n
3
2
3
᎐
᎐
᎐
᎐
4
Si(C᎐C) Ph (n = 2 or 3), Ru(C᎐CC H C᎐CSiMe -4)(PPh ) Cp
᎐
᎐
n
6
3
3 2
᎐
᎐
᎐
from Me SiC᎐CC H C᎐CSiMe -4 and [Ru(PPh3)2Cp]2-
{µ-(C᎐C) } from Me Si(C᎐C) SiMe (n = 2 or 3) is more difficult
᎐
3 3
᎐
᎐
3
6
4
3
᎐
᎐
᎐
including the preparations of Fe(C᎐CC᎐CH)(CO) Cp and
᎐
᎐
᎐
2
n
n
19
᎐
᎐
᎐
᎐
{Fe(CO) Cp} (µ-C᎐CC᎐C),
trans-Rh(C᎐CC᎐CSiMe )(CO)-
to rationalise in this manner.
In the case of Me SiC᎐CC H C᎐CSiMe -4 it may reasonably
᎐
3 6 3
᎐
᎐
᎐
᎐
2
2
3
(PPri3)2,20 trans-RuCl{C᎐CC᎐CCPh (OSiMe )}(dppm)
and
15a
᎐
᎐
᎐
᎐
᎐
4
᎐
᎐
2
3
2
the high molecular weight polymers of general form {Pt(EBu3)2-
be expected that both SiMe3 groups would display similar
reactivity towards fluoride-induced desilylation and con-
sequently that the removal of both SiMe3 groups would occur
essentially concurrently. In order to account for the formation
21
᎐
(C᎐C) } (E = P or As).
᎐
m
n
While the introduction of the terminal trialkyltin group
results in the formation of diynyl reagents of greatly increased
thermal stability when compared to the parent terminal diynyl
reagents, they still suffer from several drawbacks, not the least
of these being the extreme deliquescence of these materials and
their extreme toxicity. Furthermore, these organotin com-
pounds are often prepared from the terminal polyyne reagent,
either via a lithiation/derivatisation sequence,22 or the reaction
of SnR3(NRЈ2) with the terminal polyyne.23 These successful
applications of the trialkyltin-protected polyynes for the syn-
thesis of metal complexes prompted us and others to consider
the use of trialkylsilyl-protected polyynes directly in the prep-
aration of metal alkynyl and polyynyl complexes. The silicon-
protected compounds offer several synthetic advantages over
the corresponding tin compounds in that the silylated com-
pounds are both thermally stable and chemically robust.
Indeed, trialkylsilyl moieties lend such stability to alkynyl and
polyynyl compounds that they are widely used as protecting
groups in conventional organic acetylene and polyacetylene
᎐
᎐
of Ru(C᎐CC H C᎐CSiMe -4)(PPh ) Cp via the Lapinte mech-
᎐
᎐
6
4
3
3 2
᎐
᎐
anism the initial, monodesilylation of Me SiC᎐CC H C᎐
CSiMe -4 to give HC᎐CC H C᎐CSiMe -4 must be followed by
᎐
᎐
3
6
4
᎐
᎐
᎐
᎐
3
6
4
3
the metallation sequence with a combined reaction rate several
orders of magnitude faster than that of cleavage of the second
᎐
᎐C–SiMe bond.
᎐
3
The high yield formation of the phenyl-substituted com-
᎐
plexes Ru{(C᎐C) Ph}(PPh ) Cp and the bimetallic complexes
᎐
n
3 2
᎐
{Ru(PPh ) Cp} {µ-(C᎐C) } also poses some problems for
᎐
3
2
2
n
the reaction mechanism in Scheme 2 as the terminal diynes
᎐
᎐
HC᎐CC᎐CR (R = H, SiMe or Ph) are all thermally unstable
᎐
᎐
3
compounds which are prone to rapid polymerisation. In addi-
tion, as indicated above, 1,3-diynes have been shown to react
with metal fragments, including [Ru(PPh3)2Cp]ϩ, to give highly
reactive butatrienylidene cations [{M}᎐C᎐C᎐C᎐CHR]ϩ, rather
᎐ ᎐ ᎐ ᎐
than simple, stable vinylidene complexes.14
An alternative interpretation of these results is embodied in
the reaction mechanism shown in Scheme 3. In methanol
the Ru–Cl bond is significantly ionised, which offers a point
of entry for the silyl-substituted alkyne into the metal co-
ordination sphere, followed by, or possibly concomitant with, a
1,2-silyl shift to give a silylvinylidene. 1,2-Silyl shifts have been
reported previously.28 Nucleophilic attack by fluoride ion on the
silicon centre then generates the alkynyl complexes which, in
our systems, precipitate from the reaction mixture. In the case
of the bis(silyl) alkynes precipitation of the product acetylides
syntheses and as such they are also readily available.
᎐
In 1993 the formation of Ru{C᎐CC(O)CHMe }(PPh ) Cp
᎐
2
3 2
᎐
from the reaction of RuCl(PPh ) Cp, Me SiC᎐CC(O)CHMe
᎐
3
2
3
2
and KF in methanol was briefly described, although, to the best
of our knowlege, no subsequent reports have described this syn-
thesis in detail.24 More recently, Lapinte and co-workers25 have
described the formation of the iron() acetylide complexes
᎐
᎐
1,3-{Cp*(dppe)FeC᎐C} C H and 1,3,5-{Cp*(dppe)FeC᎐C} -
᎐
᎐
2
6
4
3
᎐
C H from methanolic solutions of FeCl(dppe)Cp* and C (C᎐
᎐
6
3
6
᎐
᎐
᎐
᎐
CSiMe3)nH6Ϫn in the presence of KF and KPF6 salts, while we
may occur either before (in the case of Ru(C᎐CC H C᎐CSiMe -
᎐
6 4 3
᎐
᎐
᎐
have mentioned the use of Me SiC᎐CC᎐CSiMe /KF in the syn-
4)(PPh ) Cp) or after (as with {Ru(PPh ) Cp} {µ-(C᎐C) }) the
᎐
᎐
3
3
3 2 3 2 2 n
26
thesis of {Ru(PPh ) Cp} (µ-C᎐CC᎐C). The Dixneuf group
reaction of the second silyl group. Dixneuf and co-workers27
have proposed a similar mechanism to explain the activation of
1-silyl-1,3-diynes by ruthenium() complexes.
᎐
᎐
᎐
᎐
3
2
2
᎐
᎐
have obtained the diynyl complex Ru{C᎐CC᎐CCPh (OSiMe )}-
᎐
᎐
2
3
Cl(PMe3)(η6-C6Me6) from the reaction of RuCl2(PMe3)(η6-
᎐
᎐
C Me ) with Me SiC᎐CC᎐CCPh (OSiMe ) in the presence of
The ease with which these compounds are obtained is note-
worthy. For example, many complexes of bifunctional dialkynes
᎐
᎐
6
6
3
2
3
both NHPri2 and NaPF6.27
3724 J. Chem. Soc., Dalton Trans., 1999, 3719–3728

View Article Online
Scheme 3
such as 1,4-diethynylbenzene have been reported in recent
times.29 While the vast majority of these complexes are sym-
metrically metallated homobimetallic complexes, Dixneuf’s
plexes. The family of symmetrical octatetraynediyl compounds
{ML }(C᎐C) {ML } ({ML } = Re(NO)(PPh )Cp*,40 Fe(dppe)-
᎐
᎐
n
4
n
n
3
Cp*,41 Fe(CO)2Cp*42 or W(CO)3Cp4) have all been prepared
using this approach. The Lewis–Johnson group has used 1,6-
bis(trimethylstannyl)hexa-1,3,5-triyne in the preparation of
platinum-containing triacetylenic polymers.21,43 We have found
that it is also possible to use the preassembled triyne com-
group have been successful in the preparation of complexes of
30
᎐
᎐
general form {ML }C᎐CC H C᎐CSiR , which are more
᎐
᎐
n
6
4
᎐
3
᎐
closely related to the Ru(C᎐CC H C᎐CSiMe -4)(PPh ) Cp
᎐
᎐
6
4
3
3 2
described here. Dixneuf’s compounds were prepared from
i
᎐
᎐
᎐
᎐
᎐
᎐
᎐
᎐
HC᎐CC H C᎐CSiPr , which is obtained in four steps from 4-
pounds Me SiC᎐CC᎐CC᎐CPh and Me SiC᎐CC᎐CC᎐CSiMe
᎐ ᎐ ᎐ ᎐ ᎐
3 3 3
᎐
᎐
᎐
6
4
3
IC6H4NH2 in 50% overall yield.31 The isolation of the asym-
metric derivative Ru(C᎐CC H C᎐CSiMe -4)(PPh ) Cp directly
as a source of the polyyn-yl and -diyl fragments. These com-
pounds are highly reactive, and derivatives such as the dicobalt
and tcne adducts are easily obtained.
᎐
᎐
᎐
᎐
6
4
3
3 2
᎐
᎐
from the symmetrical reagent Me SiC᎐CC H C᎐CSiMe ,
᎐
᎐
3
6
4
3
which is readily available on a gram scale,32 results from the low
solubility of the monosubstituted complex in the reaction
solvent, and has provided us with a useful point of entry
to the chemistry of monometallated 1,4-diethynylbenzene
complexes.33
Conclusion
The use of fluoride ion as base has allowed the syntheses
of some ruthenium acetylide, diynyl and diynediyl complexes
simply and in high yield, from trimethylsilyl-protected alkynes
or polyynes, thereby avoiding the use of unstable reagents, such
as 1,3-diynes or the corresponding lithiated or stannyl deriv-
᎐
᎐
The reaction between Me SiC᎐CC᎐CSiMe , two equivalents
᎐
᎐
3
3
of RuCl(PPh3)2Cp, KF and NEtCy2 in methanol gave the bis-
᎐
᎐
(ruthenium) diynediyl complex {Ru(PPh ) Cp} (µ-C᎐CC᎐C),
᎐
᎐
3
2
2
which precipitated from the reaction solution. This diynediyl
compound has previously been obtained from the reaction of
atives. In their reactions with cobalt carbonyls or tetra-
᎐
cyanoethene, it is the second C᎐C triple bond out from the
᎐
᎐
᎐
LiC᎐CC᎐CLi and two equivalents of the lightly stabilised
ruthenium centre which is attacked as a result of the steric pro-
᎐
᎐
complex [Ru(thf)(PPh3)2Cp][PF6].8 While the buta-1,3-diyne-
᎐
tection afforded by the two bulky PPh ligands to the C᎐C triple
᎐
3
1,4-diyl dianion may be prepared either by treatment of buta-
bond adjacent to the ruthenium. Further studies are directed
towards extending the scope of this reaction and establishing its
versatility.
1,3-diyne with two equivalents of BuLi,34 or from HC᎐CCH᎐
᎐
᎐
᎐
CH(OMe) and three equivalents of the same base,35 the method
described above allows multigram amounts of {Ru(PPh3)2-
᎐
᎐
Cp} (µ-C᎐CC᎐C) to be prepared from the stable bis-silyl
᎐
᎐
2
Experimental
General conditions
reagent, and thereby avoids the use of the potentially hazardous
buta-1,3-diyne and alkyllithium reagents.
Several complexes of phenylbuta-1,3-diyne are known. These
36
All reactions were carried out under dry, high purity nitrogen
unless otherwise stated, using standard Schlenk techniques.
Methanol was BDH AnalaR grade used as received. Light
petroleum refers to a fraction of bp 60–80 ЊC. Elemental analy-
ses were preformed by the Canadian Microanalytical Service,
Delta, B.C. Column chromatography was carried out on
alumina (Brockman Grade 1 from Merck, used as received).
Preparative TLC was carried out on glass plates (20 × 20 cm)
coated with silica gel (Merck 60 GF254, 0.5 mm thick).
᎐
᎐
᎐
᎐
include W(C᎐CC᎐CPh)(CO) Cp* and Rh(C᎐CC᎐CPh)(CO)-
᎐
᎐
᎐
᎐
3
(PPri3)2 and RhH(C᎐CC᎐CPh)(PPr ) (L) (L = CO or py),
i
37
᎐
᎐
᎐
᎐
3
2
both of which were prepared by direct reaction of the unstable
and polymerisation-prone reagent phenylbuta-1,3-diyne with a
suitable metal complex. Alternatively, the phenyldiynyl ligand
may be assembled in stepwise fashion by Sonogashira-type
᎐
᎐
coupling of the butadiynyl ligand in W(C᎐CC᎐CH)(CO) Cp
᎐
᎐
3
4
᎐
᎐
with iodobenzene. In contrast, Me SiC᎐CC᎐CPh is a therm-
ally stable material, readily prepared by coupling of PhC᎐CBr
and HC᎐CSiMe in the presence of a mixed palladium(0)–
᎐
᎐
3
᎐
᎐
᎐
᎐
3
Instrumentation
copper() catalyst as described below, or by the more tradi-
᎐
tional Cadiot–Chodkiewicz coupling of Me SiC᎐CBr with
᎐
3
Infrared spectra were obtained on Perkin-Elmer 1700 or 1720X
FT IR spectrometers, NMR spectra of CDCl3 solutions on
Bruker ACP 300 (1H at 300.13 MHz, 13C at 75.47 MHz) or
Varian Gemini 200 (1H at 199.8 MHz, 13C at 50.29 MHz)
spectrometers. Electrospray mass spectra were obtained from
MeOH solutions unless otherwise indicated. Solutions were
directly infused into a Finnegan LCQ instrument. Nitrogen was
used as the drying and nebulising gas. Chemical aids to ionis-
ation are indicated where used.6
HC᎐CPh.38 The trialkylsilyl-protected diyne may be purified by
᎐
᎐
distillation or chromatography in air. The reaction of RuCl-
᎐
᎐
(PPh ) Cp with Me SiC᎐CC᎐CPh in the presence of a fluoride
᎐
᎐
3
2
3
ion source is a very convenient route to the diynyl complex
᎐
᎐
Ru(C᎐CC᎐CPh)(PPh ) Cp 4.
᎐
᎐
3
2
᎐
The preparation of longer chain polyynyl {ML }(C᎐C) R
᎐
n
n
᎐
and polyynediyl {ML }(C᎐C) {MЈLЈ } complexes has become
᎐
n
n
m
a field of endeavour for many in recent times. Gladysz’s group
has elegantly demonstrated that a terminal ynyl ligand may be
readily extended by linking the ligand with acetylenic building
Reagents
᎐
blocks, such as Me SiC᎐CBr, using the traditional Cadiot–
᎐
3
Chodkiewicz alkyne cross-coupling protocol.39 Gladysz and
others have reported the preparation of long chain polyynediyl
complexes by oxidative coupling of two terminal diynyl com-
The compounds RuCl(PPh3)2Cp,44 Pd(PPh3)4,45 PhC᎐CBr,
46
᎐
᎐
47
48
᎐
᎐
᎐
PhC᎐CI, Me SiC᎐CPh, 1,4-(C᎐C) C H and 1,4-(SiMe3-
᎐
᎐
᎐
3
2
6
4
32
49
50
᎐
᎐
᎐
᎐
᎐
᎐
C᎐C) C H ,
PhC᎐CC᎐CSiMe ,
Me SiC᎐CC᎐CSiMe ,
᎐
3 3
᎐
᎐
᎐
2
6
4
3
J. Chem. Soc., Dalton Trans., 1999, 3719–3728
3725

View Article Online
51
52
᎐
᎐
᎐
᎐
᎐
᎐
᎐
Me SiC᎐CC᎐CC᎐CSiMe ,
HC᎐CSiMe
and HC᎐CC᎐
(PPh3)2Cp 5 (150 mg, 40%) as a brown solid. (The product was
᎐
᎐
᎐
᎐
᎐
3
3
3
53
CSiMe3 were prepared by the literature methods. Methanol
(BDH AR grade), CuI (Ajax), 1,4-dibromobenzene (Aldrich),
KF (BDH), dbu (Aldrich) and NEtCy2 (Aldrich) were used as
received. Triethylamine was dried and distilled from KOH prior
to use.
contaminated with ca. 8–10% RuCl(PPh3)2Cp as shown by its
1H NMR Cp resonance at δ 4.10.) No ES mass spectrum could
be obtained.
᎐
᎐
᎐
(f) {Ru(PPh ) Cp} (ꢀ-C᎐CC᎐C) 6. A suspension of RuCl-
᎐
3
2
2
(PPh3)2Cp (2.0 g, 2.76 mmol) in methanol (150 ml) was treated
᎐
᎐
᎐
᎐
Me SiC᎐CC᎐CC᎐CPh. A flame-dried Schlenk tube contain-
᎐
᎐
᎐
᎐
3
with Me SiC᎐CC᎐CSiMe (0.268 g, 1.38 mmol), KF (0.16 g,
᎐
᎐
3
3
ing triethylamine (20 ml) was rigorously degassed using a
freeze/pump/thaw sequence. To the amine was then added
PhC᎐CI (280 mg, 1.23 mmol), HC᎐CC᎐CSiMe (150 mg, 1.23
mmol), Pd(PPh3)4 (71 mg, 0.06 mmol) and CuI (23 mg, 0.12
mmol) and the resulting mixture left to stir at r.t. overnight. The
mixture was filtered to remove a suspension of light brown
solids, which were then washed with hexane. The filtrate was
then concentrated, and the residue purified by TLC (silica gel;
2.76 mmol) and NEtCy2 (600 µl, 3.3 mmol). The reaction mix-
ture was heated at reflux point for 18 h. After this time the
solution was deep blue over a pale yellow-orange precipitate.
The precipitate was collected by filtration, and washed with
several portions of cold methanol. The solid was purified by
flash chromatography on an alumina column (30 × 200 mm)
using light petroleum–acetone (7:3) as the eluting solvent.
Concentration of the orange fraction gave {Ru(PPh3)2Cp}2-
᎐
᎐
᎐
᎐
᎐
᎐
3
᎐
᎐
᎐
hexane, R 0.7) to give PhC᎐CC᎐CC᎐CSiMe as a light yellow
᎐
᎐
᎐
᎐
᎐
f
3
(µ-C᎐CC᎐C) 6a as a pale orange microcrystalline powder (1.3 g,
᎐
᎐
oil (78 mg, 29%). 1H NMR (CDCl3): δ 0.22 (s, 9 H, SiMe3) and
Ϫ1
1
᎐
66%). IR (Nujol): ν(C᎐C) 1970m cm . H NMR (CDCl ): δ
᎐
3
᎐
7.32–7.52 (m, 5 H, Ph). IR (CH Cl ): ν(C᎐C) 2195m, 2174m
᎐
2
2
4.17 (s, 10 H, Cp) and 7.03–7.64 (m, 60 H, Ph). ES mass spec-
and 2075s cmϪ1.
trum (MeOH): m/z 1430, [M]ϩ; 715, [M]2ϩ and 692, [Ru-
(PPh3)2Cp]ϩ. Recrystallisation of 6a from hot thf afforded
᎐
Preparation of ruthenium alkynyl and polyynyl complexes
isomer 6b quantitatively. IR (Nujol): ν(C᎐C) 1990w and 1976m
᎐
cmϪ1. 1H NMR (CDCl3): δ 4.17 (s, 10 H, Cp) and 7.03–7.64 (m,
60 H, Ph). ES MS (MeOH): m/z 1430, [M]ϩ; 715, [M]2ϩ and 692,
[Ru(PPh3)2Cp]ϩ.
᎐
(a) Ru(C᎐CPh)(PPh ) Cp 1. A mixture of RuCl(PPh ) Cp
(200 mg, 0.276 mmol), PhC᎐CSiMe (60 mg, 0.34 mmol) and
KF (16 mg, 0.28 mmol) was heated in refluxing MeOH (20 ml)
for 2.5 h. After cooling in ice, the precipitated Ru(C᎐CPh)-
(PPh3)2Cp (182 mg, 84%) was filtered off and washed with cold
MeOH and Et2O. It was identified by comparison with an
authentic sample.5
᎐
3
2
3 2
᎐
᎐
3
᎐
᎐
᎐
᎐
᎐
᎐
(g) {Ru(PPh ) Cp} (ꢀ-C᎐CC᎐CC᎐C) 7. To a methanolic (30
᎐
᎐
3
2
2
ml) suspension of RuCl(PPh3)2Cp (200 mg, 0.28 mmol) was
᎐
᎐
᎐
added Me SiC᎐CC᎐CC᎐CSiMe (60 mg, 0.28 mmol) and KF
᎐
᎐
᎐
3
3
(20 mg, 0.35 mmol). The resulting mixture was refluxed for 1 h
until all the orange RuCl(PPh3)2Cp had been replaced by a pale
green precipitate. The solution was then allowed to cool, and
the precipitate filtered off and washed with cold MeOH to give
᎐
᎐
᎐
(b) Ru(C᎐CC H C᎐CSiMe )(PPh ) Cp 2. A mixture of 1,4-
᎐
6
4
3
3 2
bis(trimethylsilylethynyl)benzene (450 mg, 1.66 mmol), RuCl-
(PPh3)2Cp (1210 mg, 1.66 mmol) and KF (98 mg, 1.66 mmol)
was stirred in refluxing MeOH (80 ml) overnight. After this
time the orange suspension had become bright yellow. The
solvent was filtered off to give a yellow powder (1280 mg, 87%).
The crude product was then chromatographed on an alumina
column eluting with acetone–hexane (3:7). Concentration of
the yellow fraction, filtration and washing the solid with hexane
᎐
᎐
᎐
{Ru(PPh ) Cp} (µ-C᎐CC᎐CC᎐C) 7 (173 mg, 87%). Crystals
᎐
᎐
᎐
3
2
2
suitable for X-ray study were obtained from CHCl3–pentane.
᎐
᎐
᎐
Reaction of Ru(C᎐CC᎐CPh)(PPh ) Cp with Co (CO) . A
᎐
3
2
2
8
᎐
᎐
mixture of Ru(C᎐CC᎐CPh)(PPh ) Cp (80 mg, 0.10 mmol) and
᎐
᎐
3
2
Co2(CO)8 (74 mg, 0.22 mmol) in benzene (10 ml) was stirred at
r.t. for 1 h. The solvent was removed, and the residue purified
᎐
᎐
gave Ru(C᎐CC H C᎐CSiMe )(PPh ) Cp 2 as a yellow powder
᎐
᎐
6
4
3
3 2
(960 mg, 64%).
by TLC (silica gel; acetone–hexane 1:4, Rf 0.6, black band)
᎐
giving Ru{C᎐CC Ph[Co (CO) ]}(PPh ) Cp 8 (70 mg, 65%).
᎐
2
2
6
3 2
᎐
Crystals suitable for X-ray study were obtained from CH2Cl2–
MeOH.
(c) 1,4-{Cp(PPh ) Ru(C᎐C)} C H 3. A mixture of RuCl-
᎐
3
2
2
6
4
(PPh3)2Cp (262 mg, 0.37 mmol), 1,4-bis(trimethylsilylethynyl)-
benzene (50 mg, 0.185 mmol) and KF (21 mg, 0.37 mmol) was
heated in a refluxing mixture of thf–MeOH (1:1, 40 ml) for
16 h. An orange precipitate formed which was collected and
᎐
᎐
᎐
Reactions with tetracyanoethene (tcne). (a) Ru(C᎐CC᎐CPh)-
᎐
᎐
᎐
(PPh ) Cp. A mixture of Ru(C᎐CC᎐CPh)(PPh ) Cp (80 mg,
᎐
᎐
3
2
3 2
washed with hexane and recrystallised (CH2Cl2–MeOH) to give
0.10 mmol) and tcne (40 mg, 0.30 mmol) in CH2Cl2 (10 ml) was
stirred at r.t. for 1 h. The solvent was removed, and the residue
purified by TLC (silica gel; CH2Cl2–hexane 1:2, Rf 0.5, deep red
᎐
1,4-{Cp(PPh ) Ru(C᎐C)} C H 3 (120 mg, 43%).
᎐
3
2
2
6
4
᎐
᎐
᎐
᎐
(d) Ru(C᎐CC᎐CPh)(PPh ) Cp 4. To a methanolic (30 ml)
band) to give Ru{C᎐CC[᎐C(CN) ]CPh᎐C(CN) }(PPh ) Cp 10
᎐
3
2
᎐
᎐
᎐
2
2
3 2
suspension of RuCl(PPh3)2Cp (810 mg, 1.12 mmol) was added
(80 mg, 90%). Crystals suitable for X-ray study were obtained
᎐
᎐
PhC᎐CC᎐CSiMe (221 mg, 1.12 mmol) and KF (65 mg, 1.12
from CH2Cl2–hexane.
᎐
᎐
3
᎐
᎐
᎐
᎐
mmol). The mixture was refluxed for 1 h when all the orange
RuCl(PPh3)2Cp had been replaced by a pale green precipitate.
The solution was then allowed to cool, and the precipitate
filtered off and washed with cold MeOH. The product was
then purified by passage through basic alumina, eluting with
(b) Ru(C᎐CC᎐CC᎐CPh)(PPh ) Cp. A mixture of Ru-
᎐
᎐
3
2
᎐
᎐
᎐
(C᎐CC᎐CC᎐CPh)(PPh ) Cp (50 mg, 0.059 mmol) and tcne
᎐
᎐
᎐
3
2
(23 mg, 0.180 mmol) in CH2Cl2 was stirred at r.t. for 30
min. The mixture was concentrated, and the residue purified
by TLC (silica gel; hexane–acetone 7:3). A green-black band
᎐
᎐
᎐
᎐
CH Cl , to give Ru(C᎐CC᎐CPh)(PPh ) Cp 4 (680 mg, 75%).
(Rf 0.8) contained Ru{C᎐CC[᎐C(CN) ]C[᎐C(CN) ]C᎐CPh}-
᎐
᎐
2
2
3 2
᎐
᎐
᎐
᎐
2
2
Crystals suitable for X-ray study were obtained from toluene–
hexane.
(PPh3)2Cp 11 (17 mg, 30%). Crystals suitable for X-ray study
were obtained from CH2Cl2–MeOH.
᎐
᎐
᎐
᎐
(c) {Ru(PPh ) Cp} (µ-C᎐CC᎐CC᎐C). A mixture of {Ru-
᎐
᎐
3
᎐
2
2
᎐
᎐
᎐
᎐
᎐
(e) Ru(C᎐CC᎐CC᎐CPh)(PPh ) Cp 5. The compounds RuCl-
(PPh ) Cp} (µ-C᎐CC᎐CC᎐C) (100 mg, 0.063 mmol) and tcne
᎐ ᎐
3 2 2
᎐
᎐
᎐
᎐
3
2
(PPh3)2Cp (327 mg, 0.45 mmol) and KF (26 mg, 0.45 mmol)
(50 mg, 0.39 mmol) in thf (10 ml) was stirred at r.t. for 30 min.
The mixture was concentrated, and the residue purified by
᎐
᎐
᎐
were added to a solution of PhC᎐CC᎐CC᎐CSiMe (ca. 100 mg,
᎐
᎐
᎐
3
0.45 mmol, freshly purified by TLC and extracted with MeOH
(30 ml)). The resulting mixture was refluxed for 4 h, allowed to
cool, then filtered to remove unchanged RuCl(PPh3)2Cp. The
TLC (silica gel; hexane–acetone 7:3). The red band (Rf 0.5)
᎐
gave {Ru(PPh ) Cp} {µ-(C᎐CC[=C(CN) ]) } 12 (75 mg, 70%).
᎐
3
2
2
2
2
Crystals suitable for X-ray study were obtained from CHCl3–
hexane.
᎐
᎐
᎐
filtrate was then concentrated to give Ru(C᎐CC᎐CC᎐CPh)-
᎐
᎐
᎐
3726
J. Chem. Soc., Dalton Trans., 1999, 3719–3728

View Article Online
Crystallography
Co2O4P4Ru. M = 1354.1, monoclinic, space group P21/n, a =
17.474(3), b = 17.164(3), c = 22.453(4) Å, β = 111.223(5)Њ, V =
6277 Å3, Z = 4, µMo = 9.1 cmϪ1, Nt = 55791, N = 11195 (Rint
0.092), No = 3240, R = 0.082, RЈ = 0.071, nν = 731, T ca. 300 K.
In consequence of weak and limited data/high ‘thermal motion’
(poor crystal quality?) ring 132 was modelled with isotropic
Full spheres of data were measured at the specified temper-
atures to 2θmax = 58Њ using a Bruker AXS CCD instrument
(monochromatic Mo-Kα radiation, λ 0.71073 Å); Ntotal data
were measured and reduced to N independent reflections, No
with F > 4σ(F) being considered ‘observed’ and used in the full
matrix least squares refinement after absorption correction.
Anisotropic thermal parameters were refined for the non-
hydrogen atoms; (x, y, z, Uiso)H were included constrained at
estimated values. Computation used the XTAL 3.4 program
system54 implemented by S. R. Hall; neutral atom complex
scattering factors were employed. Individual variations in
procedure/difficulties/idiosyncrasies are noted below.
=
thermal parameter forms.
᎐
Ru{C᎐CC[᎐C(CN) ]CPh᎐C(CN) }(PPh ) CpؒC H Meؒ
᎐
᎐
᎐
2
2
3
2
2
5
᎐
C6H14 10 ᎐C H N P Ru. M = 1122.3, monoclinic, space group
᎐
70 62
4
2
C2/c (no. 15), a = 26.078(3), b = 12.559(1), c = 37.015(4) Å, β =
110.218(1)Њ, V = 11375 Å3, Z = 8, µMo = 3.8 cmϪ1, Nt = 67495,
N = 9976 (Rint = 0.058), No = 6359, R = 0.068, RЈ = 0.092, nν =
609, T ca. 300 K. Data were weak and limited, 2θmax = 50Њ, high
thermal motion on the solvent moieties, modelled as above,
presumably being a contributing factor. Site occupancy of the
latter was set at unity after trial refinement.
᎐
᎐
᎐
Crystal/refinement data. Ru(C᎐CC H C᎐CSiMe -4)(PPh ) -
᎐
6
4
3
3 2
᎐
᎐
᎐
Cp 2 ᎐ C H P RuSi. M = 888.1, monoclinic, space group
Ru{C᎐CC[᎐C(CN) ]C[᎐C(CN) ]C᎐CPh}(PPh ) Cp
11
᎐
᎐
᎐
᎐
᎐
54 48
2
2
2
3 2
᎐
P21/c (no. 14), a = 19.420(1), b = 14.889(1), c = 17.173(2) Å,
β = 112.851(1)Њ, V = 4575.9 Å3, Z = 4, µMo = 4.7 cmϪ1, Nt =
50803, N = 8031 (Rint = 0.040), No = 5328; R = 0.058,
RЈ = 0.072, nν = 523, T ca. 300 K. The specimen was a feebly
diffracting flake, data being limited to 2θmax = 50Њ.
᎐C H N P Ru. M = 968.0, monoclinic, space group P2 /c,
᎐
1
40
4
2
a =5926.229(3), b = 16.301(2), c = 23.696(3) Å, β = 105.880(2)Њ,
V = 9745 Å3, Z = 8, µMo = 4.3 cmϪ1, Nt = 109545, N = 25078
(Rint = 0.022), No = 13808, R = 0.058, RЈ = 0.054; nν = 1160.
Phenyl ring 28 in molecule 2 was modelled as disordered over
two sets of sites, occupancies set at 0.5 after trial refinement,
both rings were refined as rigid bodies with isotropic thermal
parameter forms.
᎐
᎐
᎐
᎐
51 40
Ru(C᎐CC᎐CPh)(PPh ) Cp 4. ᎐C H P Ru. M = 815.9,
᎐
᎐
3
2
2
monoclinic, space group P21/c, a = 14.825(3), b = 14.561(3),
c = 18.613(4) Å, β = 100.446(3)Њ, V = 3952 Å3, Z = 4, µMo = 5.1
cmϪ1, Nt = 46126, N = 10005 (Rint = 0.027), No = 5644, R =
0.044, RЈ = 0.043, nν = 487, T ca. 300 K.
CCDC reference number 186/1632.
See http://www.rsc.org/suppdata/dt/1999/3719/ for crystallo-
graphic files in .cif format.
᎐
᎐
᎐
᎐
94 86
{Ru(PPh ) Cp} (µ-C᎐CC᎐C)ؒ2thf 6ؒ2thf ᎐C H O P Ru .
᎐
᎐
3
2
2
2
4
2
M = 1573.8, monoclinic, space group P21/c, a = 23.51(1),
b = 14.710(9), c = 25.874(9) Å, β = 118.11(3)Њ, V = 7894 Å3,
Z = 4, µMo = 5.1 cmϪ1, N = 14092, No = 6675, R = 0.083,
RЈ = 0.083, nν = 896.
Acknowledgements
We thank the Australian Research Council for support of this
work and Johnson Matthey plc, Reading, UK, for a generous
loan of RuCl3ؒxH2O.
For this compound and its 0.8 MeOH solvated counterpart,
data were measured using a single-counter/sequential instru-
ment to 2θmax = 50Њ at ca. 295 K; gaussian absorption correc-
tions were applied. In this compound specifically, thf solvent
residues were refined with constrained geometries, and in the
case of thf isotropic thermal parameter forms. Linewidths were
rather large throughout, perhaps a consequence of rather facile
desolvation. In the methanol solvate residues modelled as C, O
were refined with isotropic thermal parameters forms and site
occupancies set at 0.8 after trial refinement; this latter form, for
which samples are also difficult, has been previously recorded in
ref. 8, described as unsolvated (R = 0.11); the present study, in
standard space group setting, represents an improvement on the
previous effort. The cell volume of the previous (nicely precise)
definition of a 2thf solvate as a triclinic form was 2015 Å3,
larger than the present asymmetric unit ascribed as a 2thf sol-
vate also, in the monoclinic form. Asymmetric unit volumes of
the studies recorded for previous and the present unsolvated
and solvated orthorhombic forms are identical.
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᎐
᎐
᎐
᎐
86
{Ru(PPh ) Cp} (µ-C᎐CC᎐C)ؒ0.8CH OH 6ؒMeOH ᎐C -
᎐
᎐
3
2
2
3
H70P4Ru2ؒ0.8CH3OH. M = 1455.2, orthorhombic, space group
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V = 7254 Å3, Z = 4, µMo = 5.5 cmϪ1, N = 6402, No = 2457,
R = 0.058, RЈ = 0.053, nν = 424.
᎐
᎐
᎐
᎐
᎐
92 78
{Ru(PPh ) Cp} (µ-C᎐CC᎐CC᎐C)ؒ4CH Cl 7 ᎐C H Cl -
᎐
᎐
᎐
3
2
2
2
2
8
P4Ru2. M = 1793.3, monoclinic, space group P21/n [no. 14
(variant)], a = 12.408(1), b = 15.398(2), c = 21.246(3) Å, β =
97.833(2)Њ, V = 4021 Å3, Z = 2, µMo = 7.7 cmϪ1, Nt = 48326, N =
9240 (Rint = 0.044), No = 5146, R = 0.054, RЈ = 0.054, nν = 489,
T ca. 153 K.
᎐
᎐
᎐
58 42
Ru{C᎐CC Ph[Co (CO) ]}(PPh ) CpؒCH Cl 8 ᎐C H Cl -
᎐
2
2
6
3
2
2
2
2
¯
Co2O6P2Ru. M = 1186.8, triclinic, space group P1 (no. 2),
a = 11.831(1), b = 14.195(1), c = 17.632(2) Å, α = 95.453(1), β =
104.238(1), γ = 112.847(1)Њ, V = 2584 Å3, Z = 2, µMo = 11.4
cmϪ1, Nt = 30223, N = 16225 (Rint = 0.026), No = 9742, R =
0.038, RЈ = 0.046, nν= 641, T ca. 300 K. Solvent site occupancy
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᎐
᎐
᎐
74 58
Ru{C᎐CC H[Co (µ-dppm)(CO) ]}(PPh ) Cp 9 ᎐C H -
᎐
2
2
4
3
2
J. Chem. Soc., Dalton Trans., 1999, 3719–3728
3727

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Paper 9/05174K
3728
J. Chem. Soc., Dalton Trans., 1999, 3719–3728